Renewable synthesis of MoO3 nanosheets via low temperature phase transition for supercapacitor application.

2D transition metal oxides have created revolution in the field of supercapacitors due to their fabulous electrochemical performance and stability. Molybdenum trioxides (MoO3) are one of the most prominent solid-state materials employed in energy storage applications. In this present work, we report a non-laborious physical vapor deposition (PVD) and ultrasonic extraction (USE) followed by vacuum assisted solvothermal treatment (VST) route (DEST), to produce 2D MoO3 nanosheets, without any complex equipment requirements. Phase transition in MoO3 is often achieved at very high temperatures by other reported works. But our well-thought-out, robust approach led to a phase transition from one phase to another phase, for e.g., hexagonal (h-MoO3) to orthorhombic (α-MoO3) structure at very low temperature (90 °C), using a green solvent (H2O) and renewable energy. This was achieved by implementing the concept of oxygen vacancy defects and solvolysis. The synthesized 2D nanomaterials were investigated for electrochemical performance as supercapacitor electrode materials. The α-MoO3 electrode material has shown supreme capacitance (256 Fg-1) than its counterpart h-MoO3 and mixed phases (h and α) of MoO3 (< 50 Fg-1). Thus, this work opens up a new possibility to synthesize electrocapacitive 2D MoO3 nanosheets in an eco-friendly and energy efficient way; hence can contribute in renewable circular economy.

Layered Double Hydroxide-Cellulose Hybrid Beads: A Novel Catalyst for Topochemical Grafting of Pulp Fibers.

Cellulose-based materials are very attractive for emerging bioeconomy as they are renewable, inexpensive, and environmentally friendly. Cellulose beads are spherical and porous and can be highly engineered to be used as catalyst support material. This type of inorganic catalysts is cost-effective and suitable for multiple re-usage and has been rarely explored in cellulose reaction research. In this work, NiFe-layered double hydroxide (LDH) was tailor-made in situ on anionic cellulose beads to form a hybrid, supported photocatalyst for the first time. The hybrid beads were prepared in a size larger than the pulp fibers in order to make the catalysis reaction heterogeneous in nature. Hydrophilic pulp fibers were converted into hydrophobic pulp by photocatalytic topochemical grafting of ethyl acrylate using the LDH-cellulose bead catalyst. The approach identified for the modification of the pulp fibers is the "hydrogen abstraction-UV photografting" because the low-energy, UV radiation-induced grafting offers advantages, such as a reduced degradation of the backbone polymer and a control over the grafting reaction. After grafting, the pulp fibers showed increased water repellency and unaltered thermal stability, indicating the hydrophobic, plasticizing nature of the pulp, which in turn accounts for its thermoformable behavior. These acrylated pulp fibers can be further designed/customized for waterproof or oil absorption applications.

Topochemical engineering of composite hybrid fibers using layered double hydroxides and abietic acid.

Topochemical engineering of hybrid materials is an efficient way of synthesizing hydrophobic and highly tensile fiber composites by utilizing the intermolecular hydrogen bonds in natural materials. These materials include wood pulp fibers, abietic acid (resin acid) and inexpensive metal salts. In this work, a hybrid composite was created using bleached and unbleached kraft pulp fibers as cellulose platform. In situ co-precipitation of layered double hydroxide (LDH) was performed to grow LDH crystals on the surface of the cellulose fibers, followed by the immobilization of abietic acid (AA) on LDH-grafted cellulose. Here we aimed to benefit from the hydrogen bonding between -OH groups of cellulose and LDH, and the -COOH groups of AA to obtain charge-directed assembly of one material on the other material. Thus, composite hybrid fibers (C-HF) were produced and then characterized by optical (CAM), spectroscopic (XRD, IR) and microscopic techniques (SEM) to determine their average length and distribution, structure and purity, bonding, and morphology. These fibers further were tested for water contact angle (hydrophobicity), oil absorption (lipophilicity), tensile strength and ISO brightness measurements. The performance of C-HF was compared with unmodified reference fibers (REF), fibers composed with only AA (C-F) and LDH-hybridized fibers (HF). The results revealed a variety of correlations between materials and their properties due to characteristic surface morphology, functional groups, hydrogen bonding and natural co-materials such as lignin and hemicelluloses. Attractive and repulsive van der Waals forces between material entities play a crucial role in the resulting properties.

Topochemical Engineering of Cellulose-Based Functional Materials.

Topochemical engineering is a method of designing the fractionation (disassembly) and fabrication (assembly) of highly engineered functional materials using a combination of molecular and supramolecular techniques. Cellulose is one of the naturally occurring biopolymers, currently considered to be an important raw material for the design and development of sustainable products and processes. This feature article deals with new insights into how cellulose can be processed and functionalized using topochemical engineering in order to create functional fibers, enhance biopolymer dissolution in water-based solvents, and control the shaping of porous materials. Subsequently, topochemical engineering of cellulose offers a variety of morphological structures such as highly engineered fibers, functional cellulose beads, and reactive powders that find relevant applications in pulp bleaching, enzyme and antimicrobial drug carriers, ion exchange resins, photoluminescent materials, waterproof materials, fluorescent materials, flame retardants, and template materials for inorganic synthesis. The topochemical engineering of biopolymers and biohybrids is an exciting and emerging area of research that can boost the design of new bioproducts with novel functionalities and technological advancements for biobased industries.

Selective photocatalytic oxidation of benzene for the synthesis of phenol using engineered Au-Pd alloy nanoparticles supported on titanium dioxide.

The selectivity of photocatalytic phenol production from the direct oxidation of benzene can be enhanced by fine adjustment of the morphology and composition of Au-Pd metal nanoparticles supported on titanium dioxide thereby suppressing the decomposition of benzene and evolution of phenolic compounds.

Designer titania-supported Au-Pd nanoparticles for efficient photocatalytic hydrogen production.

Photocatalytic hydrogen evolution may provide one of the solutions to the shift to a sustainable energy society, but the quantum efficiency of the process still needs to be improved. Precise control of the composition and structure of the metal nanoparticle cocatalysts is essential, and we show that fine-tuning the Au-Pd nanoparticle structure modifies the electronic properties of the cocatalyst significantly. Specifically, Pd(shell)-Au(core) nanoparticles immobilized on TiO2 exhibit extremely high quantum efficiencies for H2 production using a wide range of alcohols, implying that chemical byproducts from the biorefinery industry can be used as feedstocks. In addition, the excellent recyclability of our photocatalyst material indicates a high potential in industrial applications. We demonstrate that this particular elemental segregation provides optimal positioning of the unoccupied d-orbital states, which results in an enhanced utilization of the photoexcited electrons in redox reactions. We consider that the enhanced activity observed on TiO2 is generic in nature and can be transferred to other narrow band gap semiconductor supports for visible light photocatalysis.

High activity redox catalysts synthesized by chemical vapor impregnation.

The use of precious metals in heterogeneous catalysis relies on the preparation of small nanoparticles that are stable under reaction conditions. To date, most conventional routes used to prepare noble metal nanoparticles have drawbacks related to surface contamination, particle agglomeration, and reproducibility restraints. We have prepared titania-supported palladium (Pd) and platinum (Pt) catalysts using a simplified vapor deposition technique termed chemical vapor impregnation (CVI) that can be performed in any standard chemical laboratory. These materials, composed of nanoparticles typically below 3 nm in size, show remarkable activity under mild conditions for oxidation and hydrogenation reactions of industrial importance. We demonstrate the preparation of bimetallic Pd-Pt homogeneous alloy nanoparticles by this new CVI method, which show synergistic effects in toluene oxidation. The versatility of our CVI methodology to be able to tailor the composition and morphology of supported nanoparticles in an easily accessible and scalable manner is further demonstrated by the synthesis of Pdshell-Aucore nanoparticles using CVI deposition of Pd onto preformed Au nanoparticles supported on titania (prepared by sol immobilization) in addition to the presence of monometallic Au and Pd nanoparticles.

Switching-off toluene formation in the solvent-free oxidation of benzyl alcohol using supported trimetallic Au-Pd-Pt nanoparticles.

Trimetallic Au-Pd-Pt nanoparticles have been supported on activated carbon by the sol-immobilisation method. They are found to be highly active and selective catalysts for the solvent-free aerobic oxidation of benzyl alcohol. The addition of Pt promotes the selectivity to the desired product benzaldehyde at the expense of toluene formation. Detailed aberration corrected STEM-XEDS analysis confirmed that the supported particles are indeed Au-Pd-Pt ternary alloys, but also identified composition fluctuations from particle-to-particle which vary systematically with nanoparticle size.

Promotion of phenol photodecomposition over TiO2 using Au, Pd, and Au-Pd nanoparticles.

Noble metal nanoparticles (Au, Pd, Au-Pd alloys) with a narrow size distribution supported on nanocrystalline TiO(2) (M/TiO(2)) have been synthesized via a sol-immobilization route. The effect of metal identity and size on the photocatalytic performance of M/TiO(2) has been systematically investigated using phenol as a probe molecule. A different phenol degradation pathway was observed when using M/TiO(2) catalysts as compared to pristine TiO(2). We propose a mechanism to illustrate how the noble metal nanoparticles enhance the efficiency of phenol decomposition based on photoreduction of p-benzoquinone under anaerobic conditions. Our results suggest that the metal nanoparticles not only play a role in capturing photogenerated electrons, but are strongly involved in the photocatalytic reaction mechanism. The analysis of the reaction intermediates allows us to conclude that on M/TiO(2) undesired redox reactions that consume photogenerated radicals are effectively suppressed. The analysis of the final products shows that the reusability performance of the catalyst is largely dependent on the pretreatment of the catalyst and the identity of the metal nanoparticle. Interestingly, the as-prepared Pd and Au-Pd decorated TiO(2) materials exhibit excellent long-term photoactivity, in which ~90% of the phenol can be fully decomposed to CO(2) in each cycle.

Facile removal of stabilizer-ligands from supported gold nanoparticles.

Metal nanoparticles that comprise a few hundred to several thousand atoms have many applications in areas such as photonics, sensing, medicine and catalysis. Colloidal methods have proven particularly suitable for producing small nanoparticles with controlled morphologies and excellent catalytic properties. Ligands are necessary to stabilize nanoparticles during synthesis, but once the particles have been deposited on a substrate the presence of the ligands is detrimental for catalytic activity. Previous methods for ligand removal have typically involved thermal and oxidative treatments, which can affect the size or morphology of the particles, in turn altering their catalytic activity. Here, we report a procedure to effectively remove the ligands without affecting particle morphology, which enhances the surface exposure of the nanoparticles and their catalytic activity over a range of reactions. This may lead to developments of nanoparticles prepared by colloidal methods for applications in fields such as environmental protection and energy production.

Solvent-free oxidation of primary carbon-hydrogen bonds in toluene using Au-Pd alloy nanoparticles.

Selective oxidation of primary carbon-hydrogen bonds with oxygen is of crucial importance for the sustainable exploitation of available feedstocks. To date, heterogeneous catalysts have either shown low activity and/or selectivity or have required activated oxygen donors. We report here that supported gold-palladium (Au-Pd) nanoparticles on carbon or TiO(2) are active for the oxidation of the primary carbon-hydrogen bonds in toluene and related molecules, giving high selectivities to benzyl benzoate under mild solvent-free conditions. Differences between the catalytic activity of the Au-Pd nanoparticles on carbon and TiO(2) supports are rationalized in terms of the particle/support wetting behavior and the availability of exposed corner/edge sites.

Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization.

We report the preparation of Au-Pd nanocrystalline catalysts supported on activated carbon prepared via a sol-immobilization technique and explore their use for the direct synthesis of hydrogen peroxide and the oxidation of benzyl alcohol. In particular, we examine the synthesis of a systematic set of Au-Pd colloidal nanoparticles having a range of Au/Pd ratios. The catalysts have been structurally characterized using a combination of UV-visible spectroscopy, transmission electron microscopy, STEM HAADF/XEDS, and X-ray photoelectron spectroscopy. The Au-Pd nanoparticles are found in the majority of cases to be homogeneous alloys, although some variation is observed in the AuPd composition at high Pd/Au ratios. The optimum performance for the synthesis of hydrogen peroxide is observed for a catalyst having a Au/Pd 1:2 molar ratio. However, the competing hydrogenation reaction of hydrogen peroxide increases with increasing Pd content, although Pd alone is less effective than when Au is also present. Investigation of the oxidation of benzyl alcohol using these materials also shows that the optimum selective oxidation to the aldehyde occurs for the Au/Pd 1:2 molar ratio catalyst. These measured activity trends are discussed in terms of the structure and composition of the supported Au-Pd nanoparticles.